DE2200984A1 - Isocyanuric acid derivatives and process for their preparation - Google Patents

Description

DR. BERG DIPL.-ING. STAPF

PATENT LAWYERS
8 MUNICH 8O, MAUERKIRCHERSTR. 45

Dr. Berg Dipl.-Ing. Stapf, 8 Munich 80, Mauerkircherstraße 45

Your mark Your letter Our mark

Date 1 ul JaD. 1972

Lawyer file 22 004
Be / Sch

Monsanto Company St. Louis, Missouri / U.S.A.

"Isocyanuric Acid Derivatives and Processes too their manufacture "

The present invention relates to a new group of isocyanuric acid derivatives and processes for the preparation of such Links. In particular, the present invention relates as a main object to those containing phosphorus Isocyanuric acid derivatives and processes for their preparation.

Case 3099 -2-

209830/1197

The present invention relates to a new and valuable one Group of isocyanuric acid derivatives of the following general jj'or.inel

0 S.
■ N -
t GH ₂ OH ₂ N H 0 OR ₃ Il G = O Il / N H ₂ P -
I. HN
• 0 OR _x O = G ' Nsr ' ^H 1 Il N ι
H P -
I. OR

where R ^ and S ₀ independently of one another, identical or different and can be hydrogen and / or organic radicals, the radicals R ₅ and R _{4 can be} identical or different and metal ions, hydrogen and / or alkyl, alkenyl, aryl , Alkylaryl- _r cyclic and / or alicyclic groups can be. The Iieballionen designated advance derived from metals for which, without it, to restrict "alkali metals such as sodium _r lithium and potassium, alkaline earth metals such as calcium and magnesium, aluminum, zinc, cadmium, manganese, nickel, cobalt, Ger, Xilei, tin, iron , Chromium and / or mercury belong .. Also belong to this ammonium ions and Älkylaniinoniuraionen. In particular, those alkylammonium ions derived from amines having a lower molecular weight, such as below about 300 and im. special are the allylamines, alkylenamines and alkanolamines with a content of not more than two amine "." ■ ■ ■; . ■ .- ■ ■;.-'-. ■;, ^"■ -3; ■ '■ ■ .;;; ■ _■;...".

209Ö30 / 1197 /

groups such as ethylamine, diethylamine, propylamine, propylenediamine, hexylomiu, 2-iLthylhexylariiin, rj-ijutyläthanolymin, Triethanolamine and the like are the preferred amines. Ls it should be pointed out that those metal ions are preferred which in combination with one in for the desired For the purpose of creating sufficient concentrations of water-soluble balz - -.

The formula I includes esters, partial esters, salts, par- : - tial salts, acids and partial acids. If R ^, Ep, R * and / or R ^. is an organic group, those are preferred! οubstituents (or groups):

(a). AIIqI with about 1 to about 10 carbon atoms ;

(d) alkenyl - having from about 1 to about 16 carbon atoms;

(c) aryl - phenyl, liaphtayl, anttiryl or .pneuantliryl;

;. . "Cd) alkylaryl - hydroxy, halogen, ii lower alkyl with Ί to ■■ "'." ; .- .CAllcaryl) ..: -..-

\. -. about 6 carbon atoms and amino-suD-substituted ·. Pheu.yl, i <japh.thyl, anthryl or phenanthryl;

">; r ^ v -" -Ce) - cycliscne. - with about 4 to about & carbon - ,, ■ - ■ "" - "■■ - ■.., atoms, whereby in the ring either an oticK material, ·. ■ '- ■■ -. ochulphöl- _f oxygen - or Ptiosphoratom can be present and _., -. "■

2 0 9 8 3 0/1197 COPY

(f) alicyclic -wit a content of about 4 to about 10 carbon atoms.

It should be noted that all compounds that fall within the scope of the preceding general formula I, are referred to here according to their type as "isocyanuric acid derivatives"; in other words, apart from the acids likewise the salts and esters and physical and chemical mixtures thereof as a whole as isocyanuric acid derivatives designated.

In general, the isocyanuric acid derivatives are prepared in such a way that one with one another under certain conditions conditions

(a) a phosphorus-containing material, namely orthophosphorous acid, a combination of PCl ^ and H ₀ O and a dialkyl phosphite ester,

(b) an aldehyde or a ketone and

(c) 2-Arain ο eth, /! isocyanuric acid, i.e.

Il

HW υ - CH ₀ CH ₀ NH ₀

ι ι cd cL

O = C C = O

implements.

-b-

209830/1 197

It has been found that if one uses a mixture of (a), (b) and (c) and subjecting the mixture to reaction conditions, an isocyanuric acid derivative is formed may that has at least one N-C-P bond.

The previously designated 2-aminoethyl isocyanuric acid, which is one of the basic starting materials in relation to the Manufacture of the isocyanuric acid derivative used in the area the! Formula I fall, is prepared by reacting cyanuric acid with ethyleneimine according to the process by N. Hilstein, Journal of Chemical Engineering Data, Vol. 13, No. 2, page 275, April 1968, referring to this publication is referred to here.

Aldehydes and ketones (ie, compounds collectively referred to herein as organic carbonyl compounds) that can be used in processes of this invention for making isocyanuric acid derivatives include all compounds of the general category (H) ₀

Il

R ₁ -CR ₂

where R _x and Rp can be identical or different and are hydrogen and / or organic radicals (as explained above). When R. is hydrogen, the material represented by general i'Ormel II is an aldehyde. If both radicals R1 and R2 are organic radicals, it is

-ti-

209830/1197

a ketone. Examples of some aldehydes useful in practicing the methods of the present invention include formaldehyde (such as paraformaldehyde), acetaldehyde, 2-bromoacetaldehyde, uaproaldehyde, glycotinaldehyde, grotonaldehyde, 2,2-dichloroaldehyde, uluteraldehyde, p-tolualdehyde, benzaldehyde, 3 -Glorobenzaldehyde, iiaphthaldehyde, anthraldehyde, 2-furaldehyde, tialonaldehyde, phthalaldehyde, 3.5-dibrotuphthalaldehyde, 1-glycohexene-1-carboxaldehyde, 3-quinolinecarboxaldehyde, 3-aminobenzaldehyde, LO-iiOrmylpropyl) phthalimide, etc. In this compound Aldehydes should be pointed out that they can be used as such or mixed with alcohols, for example, to facilitate the handling of the reaction mass, temperature control and the prevention of foaming, // if, for example,! Ö'orraaldehyde is selected, l'Orraalin, that is a trademark for a 2'7 / & ige (United States) or. 40ibige (British) sormaldehyde solution can be used. In general, these types contain solutions of un- ■ ferry 0 to about WYD> methanol. ■ - .. _

Typical ketones that can be used include acetone, methyl ethyl ketone, 2-pentanone, j-enenone, 1-chloro-2-propanone, butyron, i-bromo-7-nitro-r-heptanone, acetophenone, p -xiroin-a-chloroacetophenone, 5 -.? ^ »o-Tebrahydro-'l-isobubyronaphthon, Capriphenon, α, α-JJiniebtiylsbearophenon, -i-Gyclohexyl ^ methyl-i-propanone, 1- \ 2-i ^'l ur _t / l; -1-bubanou _ii .

2.0 9 8 "TO / ΊΊ ·) Τ ■■■■ - ■" ■■ '■ · - ■ >> ■■

• 1- (5-quinolyl) -1-pentanone, 2-Acet;.> Lchrysen, 4-ßrombenzophenon, 2.4-i ^J entandion, '^ Λ- diacetyl-2 ^ - hexanedione, 3-cyclohexene-1-on, 2 (J) -pyridone, 2-acetonylcyclohexanone and the like.

.- • It- should be noted that the specific examples the aldehydes and ketones, as noted above, are not the only compounds used to make them of the novel compounds of the present invention can be used. It should be pointed out that there is a there is a very wide range of raw materials that can be used. For example, the examples given organic radicals such as aliphatic hydrocarbyl, alicyclic, aryl, alkylaryl, heterocyclic, substituted aliphatic hydrocar'oyl, substituted alicyclic, have substituted aryl, substituted alkylaryl and substituted heterocyclic radicals, these radicals They can be both saturated and also unsaturated

■ can contain straight or branched chainsu. Organic itest that also contain "rings" are explained above.

- "■ tert. Subordinate, for example 2 to 5 or even more ': ; Hinge euthanasia.

.. The invention will be voided / ended. '

\ Because of factors "like diy steric hindrance that significant '· - ;; ".; Can be. If you manufacture isocyanuric acid ·· vateu with a relatively .high molecular weight can be predicted

^ '-' ^: Js: ^ ~ ;, - ν, - '''■ · ■■' · ■■■ '■■■ ■ —ü—

2 098 3 0/119?

should contain the aldehydes which will find most extensive use in the practice of the invention no more than 30 carbon atoms, while the ketones, which are most widely used here, usually contain no more than 20 carbon atoms.

If it is desired to prepare the ester form of the compounds falling within the scope of Formula I, then the corresponding dialkyl phosphite ester, (RO) pPHO, wherein R is an alkyl group having 1 to 20, preferably 1 to 8 carbon atoms instead of the orthophosphorous Acid is used as the phosphorus-containing species.

Orthophosphorous acid, by the following formula III explained is available in stores.

Cm) _H

HPO
0

For ease of description, orthophosphoric acid is used here generally as a phosphorus-containing reactant designated,

it can be used in the methods of the present invention either even as an acid or in the form of its salts, like theirs l-iono or dianimonium salts, and as hono or dialkali metal salts be used 'when orthophosphorous acid

209830/1197

is used in the salt form, there will usually be an amount of additional acid sufficient to provide the It is used to effectively convert the salt form into the more reactive orthophosphoric acid. (The use of these "additive" acids The methods of this invention will be discussed in detail later).

It should be noted that while EUP (X is used in this form, the individual components PCl ^ and H ₂ O, which react to form tUPO, can be used separately, that is, can be added at different points in the process.

Usually at least one of each of the materials intended to be reacted, i.e., those mentioned above under (a), (b) and (c) are given, subjected to an intermediate reaction to form one of the isocyanuric acid derivatives, why they are simply together in certain relative proportions (the relative proportions later will be described in detail), preferably in an acidic aqueous medium, mixed and usually sufficient be subjected to an elevated temperature for a long time, to cause the desired response. At room temperature, the speed of the intermediate reaction is this Materials low. (If time is not an issue, the reaction can be carried out at 25 ° C or below). Increasing the temperature generally leads to the

■ -10-

209830/1197

increasing the rate of the desired reaction so that usually the temperature of a mixture of phosphorous acid, 2-aminouthylisocyanuric acid and an aldehyde or ketone is maintained above about 70 ° C, the rate of its intermediate reaction is sufficiently high that conventional mixing and handling equipment is used can to produce the isocyanuric acid derivatives continuously and at technically affordable costs, if desired. It was further found that by increasing the reaction temperature the process of this invention (in the temperature range above about 75 G up to about 200 ⁰ G / the latter temperature being the spontaneous decomposition temperature for orthophosphorous acid at atmospheric pressure /) a fairly rapid increase in the Experience the speed of the desired reaction. It is therefore preferred for practical purposes that the reaction temperatures for the formation of the isocyanuric. Acid derivatives, when orthophosphorous acid is used in the methods of this invention, is above about 85 ° C. Temperatures in this preferred range '"■ (ie, about OE5 ° C to about 200 ⁰ G) to readily halten'des reflux aqueous reaction mixtures at, be kept above or below atmospheric pressure, has expired until the desired reaction." ■ ";■; ■■ "-."

It was surprising that the pr, value of the reaction medium an obviously meaningful - Eitif ImJ on the speed

"209830/1197 '

COPY ■ ·

the ability of the desired x-action. It has been found, for example, that the rate of the desired reaction in Geraischen (which contain 2-aminoethylisocyanuric acid, l'ormaldehyde and orthophosphorous acid in a molar ratio of about 1: 2: 2) is low with a p ^ value above about 4- . Possibly one reason for the slow rate of the desired reaction in reaction media with p ^ values above about 4 is that a competing reaction (the oxidation of orthophosphorous acid to orthophosphoric acid) obviously takes precedence over the desired intermediate reaction of orthophosphorous acid in these systems with the aldehyde or ketone and 2-aminoethyl isocyanuric acid. It is therefore preferred that the ρ, τ value of the reaction mixture (of orthophosphorous acid plus aldehyde or ketone plus 2-aminoethyl isocyanuric acid and usually a little water) be below about 4 and preferably about 2 for optimal results in practice -I ¹ Un ^ ^ he present invention to -access. If one of the salts of orthophosphorous oUure as raw material

'is used and when the ratio of reactive .- ■ gen 2-Aminoätayiiöocyanuräure to orthophosptioriger acid

"in the Ke'a ^ t ion ügemiü cn is relatively high, is of the" Na ral "or usual p ,, - v ^T ert of Reaktiousgemiscns or KeaKtionsmediumo in ell _t; ei:. a U not in the preferred L. However, the pj - »vert of the iteaktionsuiediuiiiij .iii.the v / irlvs ^ msten area. d / i can be adjusted by

'.:': '■ - "Y:? - ... \ ·, -'. - ■■ '■ ■ · .- ~' ^] 2- : ■ .. '209830/1197 _: ■■■ - ■■>'',:. -

any of the conventional acids which have the ability to reduce the py of the reaction medium are added to the system to lower. For example, hydrochloric acid, sulfuric acid, hydrobromic acid, phosphoric acid and sulfonic acids, as well many other acids can be used for this purpose. Another example of creating a low p ^ value and also to use a halide ion as a catalyst (discussed later) is to use a halide salt and an acid. These two ingredients alone produce the desired result; however, they can with each other react to form a salt and a hydrogen halide which also produce the end result. For example, the use of sodium chloride and sulfuric acid results in the formation of sodium bisulfate and hydrogen chloride.

Usually the desired reaction becomes quite complete under optimal reaction conditions in a reasonable and technically feasible time, for example expire in less than 3 hours when relatively low molecular weight isocyanuric acid derivatives are prepared should be. When generally relatively lower reaction temperatures and when the aldehydes and Relatively higher molecular weight ketones (as raw materials) are used in the processes provided here slightly longer reaction times are required, in order to obtain optimal yields of the desired product.

-13-

209830/1197

However, usually should not be more than about 5 to Approximately 7 hours are required for the intended reaction to proceed under good reaction conditions, regardless of which of the raw materials described above are used. On average it can be said will be that under optimal reaction conditions, generally from about several minutes to about 3 Hours are required to produce fairly pure isocyanuric acid derivatives to manufacture.

It has been stated above that there will usually be at least some water in the reaction medium. While it is not a requirement that water be present, the presence of at least some water has been found to be essential to factors (during and after the reaction) such as keeping the reactants in solution, easy handling of the reaction medium, easy maintenance of the desired reaction temperature (by refluxing as described above), easily maintaining sufficient heat transfer in the reaction mixture, lowering the viscosity of the reaction product, etc. It is, therefore, desirable that $ water is at least about 5 wt. (Based on the total weight of the introduced into the reaction mixture crude reaction materials) is · present and preferably at least about 15 wt.% Water in the reaction mixture before this temperatures above about 9O ⁰ G exposed for a long time.

-14-

209830/11 * 7

Additional water can also be added to the reaction medium from time to time as and when necessary.

The methods of this invention can be performed with conventional, readily available chemical processing equipment be performed. For example, a conventional heated glass-lined mixing (reaction) vessel, which is equipped with a reflux condenser and a fairly efficient stirrer, advantageous for Carrying out any of the preferred embodiments of the invention described in the examples below Invention can be used.

The orthophosphorous acid, 2-aminoethylisocyanuric acid and aldehydes or ketones to which this invention relates can be processed in various ways Wise are mixed with each other, this depending notably on the advantages derived from the invention can be. For example, they can simply be used in suitable proportions (the proportions below are discussed) are poured together into a mixing vessel, mixed and then heated to the reaction temperature. Or the ingredients can be heated individually before they are mixed together. (This particular one Process is useful when using higher molecular weight solid aldehydes and ketones.

-15-

220098A

can therefore be melted before they are introduced into the reaction vessel). The 2-alcohol ethyl isocyanuric acid can be used in the form of their acid salts. Sometimes it is useful and desirable to use 2-aminoethyl isocyanuric acid to mix with the phosphoric acid before it is heated well above room temperature; this is particularly the case when the 2-aminoethyl isocyanuric acid is not used in the form of the salts.

If aldehydes or ketones with boiling points below the temperatures at which this invention is carried out are used in the practice of this invention, much better yields of the desired isocyanuric acid derivatives (based on the amount of aldehyde or ketone added to the reaction vessel) can usually be obtained if the aldehyde or the ketone is slowly (for example from about 1C minutes to about 5 hours) added to the mixture of orthophosphorous acid and 2-aminoethylisocyanuric acid, while the temperature of the mixture is kept in the desired range, for example when an aqueous solution from 1 Hol 2-alcohol ethyl isocyanuric acid, 2 hol orthophosphorous acid and 2 moles of formaldehyde (theoretically calculated for the production of 1 mole of isocyanurylethyliminodi- (ffiethjlenphosjjhonsäure) at about 100 to HO ⁰ C for a longer time (to ensure a "complete" reaction), are kept less than 0.5 get the desired product manufactured, however, the same

-16-

209830/1197

Amount of formaldehyde slowly (i.e. for about 65 minutes) a mixture with the same amount of water, 1 mole 2-Aminoethylisocyanuric acid and 2 moles of phosphorous acid were added at a temperature of about 100 to 110 ° C more than 0.50 moles of the desired product is produced. It is therefore in the practice of this invention, the slow addition of the aldehyde or ketone to a hot mixture of phosphorous acid and 2-aminoethylisocyanuric acid a particularly preferred embodiment.

According to the present invention, this gives isocyanuric acid derivatives, that one (a) the phosphorus-containing material, for example orthophosphorous acid and (b) a Aldehyde or a ketone with (c) 2 ^ - Am in ο ethyl isocyanuric acid in a molar ratio of approximately 2: 2: 1. In the methods of the present invention, sometimes an excess of aldehyde or ketone (above the molar ratio 2: 1 ^ idehyde or ketone to 2-aminoethyl isocyanuric acid /) can sometimes be used advantageously. An excess of orthophosphorous acid, for example about 1 to about 100 wt. # Can also be used in these procedures. However, if the molar ratio 2-Aminoethyl isocyanuric acid is increased to orthophosphorous acid and aldehyde or ketone above 1: 2: 2, secondary reaction products are formed. Therefore, if one wishes to obtain a relatively pure isocyanuric acid derivative by the method of the previous

-17-

present invention, it is preferred that the molar ratio of 2-aminoethylisocyanuric acid to orthophosphorous acid Acid in the reaction mixture approximately 1: 2 and that the molar ratio is 2-atninoethyl isocyanuric acid to aldehyde or ketone in the reaction mixture roughly 1: 2 is.

One reason why the yields are desirable Isocyanuric acid derivatives in general usually do not. $ 100 of the theoretical amount in the methods of this invention are, is that in addition to the desired .Reaktion to form the N-C-P bond, the orthophosphorous Acid as well as an oxidation reaction (with formation of orthophosphoric acid) under the reaction conditions, that promote the desired response is subject. Because in most cases the presence of orthophosphoric acid not particularly in the terminal isocyanuric acid derivatives is harmful, one generally only has to provide an excess of orthophosphorous acid in the reaction medium, to compensate for this "loss" of orthophosphorous acid for the desired reaction. (The usage an excess of acid, but is currently expensive). It However, it was found that the presence of at least a catalytic amount of halide ions in the reaction mixture (of 2-Atninoäthylisocyanuräure, orthophosphorige Acid, aldehyde or ketone and usually water) the oxidation of the orthophosphorous acid in ortho-

-18-

209830/1197

inhibits phosphoric acid and thus makes it possible to produce relatively more of the desired isocyanuric acid derivative from the given reaction mixture than would be possible without the halide ions. Obviously, any simple halide ion can be used to effect the inhibition described above, although chloride is preferred for economic purposes. Obviously, the halide ion can be introduced into the reaction mixture in any manner without materially affecting the advantages achieved in practicing the present invention, provided that it is introduced into the reaction mixture before its temperature has risen to about 50 ° increased or-before it is held more than a few minutes at 7O ⁰ C. For example, the halide ion can be added in the form of a hydrohalic acid such as HCl, HBr, HJ, etc. or as an inorganic salt such as iNaCl, KCl, NaBr, CaCl4 and the like. Another suitable option is to use the hydrogen chloride salt of 2-aminoethyl isocyanuric acid. As mentioned later, a mixture of a non-halide containing acid and a halide salt can be used to achieve the desired end result. It has been found that even very small amounts of halide ions in the reaction mixture inhibit the oxidation of the orthophosphorous acid to some extent. Excellent results can be achieved when sitting in the reaction table

-19- 209830/1197

about 0.01 to about 10, and preferably at least about 0.5 weight percent halide ions are used. Halide ions in excess of these levels can be present without any discernible deleterious effect on the methods of the invention. As a practical matter, however, generally no more than about 20 weight percent halide ions are used in the processes.

The acid and salt forms of the isocyanuric acid derivatives im Under the general i'oruiel I of the present invention have excellent utility in the treatment of water or aqueous systems and serve both as sequestering agents such as "thBshold" agents. It should be noted that the term "threshold", as used here, refers to the chemical and / or physical phenomenon that is less than ■ stoichiometric amounts of the respective isocyanuric acid derivatives effectively prevent the precipitation and / or the crystal forms of various salts of metal ions such as Calcium, iron, copper and cobalt can change. In other words, it is the "threshold" treatment of water a process in which less than the stoichioccetric add to the detergent Vfuctis to affect crystal nuclei and thus the Avoid deposition of insoluble precipitates. The uezeicnnuii: -, · is used in the .cehoudlung of Water is used with jrol ^ phoö ^ naten and they are closer

209830/1197

in U.S. Patent 2,030,316 and in the article von ßeitmeier and Buehrer in the Journal of Physical Chemistry, . Volume 44, pages 535 to 574 (1939). Another Explanation of the threshold effect is given in the publications described by Hatch and Kice in Industrial Engineering and Chemistry of January, 1939 and August 1945 “To the aforementioned publications is referred to here.

The acid and ester forms of isocyanuric acid derivatives, those falling within the scope of general formula I have excellent suitability in the area of fire retardancy Cellulose materials and thus have a specific puncture as a fire retardant.

In the following examples, all '!' Refer to haste on weight unless otherwise stated.

201630 / Π 17

example 1

Approximately 1480 ml of N.N-dimethylformamide are placed in a 2-1 flask (DMl) and 129 g of cyanuric acid. While stirring the mixture, a charge of about 43 g of aziridine (ethyleneimine) dissolved in 150 ml of DME dropwise added over about 45 minutes. The temperature of the reaction mixture increases from about 27 G to about 29 C. During the addition it becomes a fine white color Precipitation formed. The overall reaction mixture becomes Stirred continuously for 12 hours and then filtered .. The resulting wet cake (154 g) is washed with absolute ethanol washed and then dried, yielding 125 g of product which appears as a fine white powder. The yield is about $ 72.7 of the theoretical amount and that Product is called 2-Aininoäthylisocyanuräure the following J'ormel

Il

HN iV - GH ₀ GH ₀ NH ₀ I, 222

O-G G = O

I.

analyzed. This example shows the preparation of one of the starting materials used to make the new Compounds within the framework of the general formula I are required.

209830/1197

Example 2 "". :: .- ".". ^: . - ■ "

In a 2 1 flask with toiasserkünler and. i 'dropping funnel become -approximately 96 g (0.82 tiol) yO ^ ige orthophosphorus Acid and 84 g "(0.85 mole) 37 # hydrochloric acid were introduced. The mixture obtained in the 2 l flask is then heated to the boil while adding about 2.5 g (0.17 WoI) that prepared according to the previous example 1 2-Aminoethyl isocyanuric acid for about 30 Minutes are added. About 60 ml of water will be then (after the 30 minute addition) in the. jxeaktions- ' flask added to obtain a homogeneous clear solution which has a boiling point of approximately 108 0.

The clear solution obtained in the flask is kept at the boil and after about 3 hours about 27 S (0, 90 mol) of paraformaldehyde are added. After these 3 hours have ended, the reaction mixture, which is a clear solution, is cooled to 25 ° C. A portion (50 g of approximately 295 g) of the solution is taken under. Stir in 100 ml of methanol -: -. "...,", poured and a white bodice is obtained. After filtering, the cake is slurried again in methanol, filtered and washed in the filter with methanol. ; Hach:. Drying gives ".approximately; 2.0 gweilie residual stroffe. The; '";; :. The entire batch gives a yield of approximately "11.8 g *". And this eatspricat 19, "3Z". A theoretical amount based on the 2-aminoabylisocyanuric acid used. The white

Wej'osbsboffe are analyzed for what purpose the nuclear magnetic

209830 / Π 97. '

- ^: - 220098A

•. - - 22 -

see. resonance spectra (KMK) (which prove the presence of the ii-CP. bond) and the clarification analysis used. The white solids obtained essentially contain Isocyanurylüth _t y ^r liminodi (methylenephosphonic acid) of the following OK

I. I. H H - N H 0 OH : .- ο · H ft f \
o = U ι
- U ι
- (J I. π Il t _ · ^ α —— ρ - ■ "- c H M. ^^ ι ι χι * - \ H OH 1 H 0 OH 0 = 0 ι Il P -
I. H OH

found ^Y / o theoretical % 24.67 23.3 14.3 17.2 14.1 15.6 5.16 3.9

The elementary analogy of the vast solids is:

'i'o C

$> P

5 »K

P H

The previous analysis shows that the white material has some Contains impurities. The reaction product is as a sequestering agent, as indicated in Example 7, suitable »''; ■ · · / ■. . '- "■'.

Example 3 . In a 2 1 flask described in Example 2

about 9o g (o _r 82 mol) of 70 / o and orthophosphorous oäure

_ν ; 209830/1197

capy ^^ "'."

84 g (0.85%) 37% hydrochloric acid were introduced. The mixture contained in the 2 liter flask is then heated to the boil while approximately 28.5 g (0.17 mol) of 2-Aminc ™ ethyl isocyanuric acid, which was prepared as in Example 1 above, is added. The addition takes place over 30 minutes. Then (after the $ 0-minute addition) are introduced into the Heaktionskolben to obtain a homogeneous solution with a boiling point of about 108 ⁰ C for about öü ml water.

The clear solution obtained in the flask is kept boiling and it will be over the course of about 3 hours 95 g (0.90 mol) of benzaldehyde were added. After the 3 hours have elapsed, the reaction smell becomes clear Solution is cooled to 25 ° C. One part (50 g of approx 363 g) of the solution is poured into 100 ml of methanol while stirring poured and a white precipitate is obtained. After filtering, the cake is slurried in methanol and filtered and washed in the filter with methanol. After drying, several g of white solids are obtained. The white ones

/ j1

Solids are analyzed, for which purpose the P "^ nuclear magnetic Resonance spectrum (KMK) (which shows the presence of N-C-P bonds) and Eleraentaranalysis are used. The white solid obtained essentially contains the isocyanuric acid derivative represented by the following formula

209830/1197

C-Hn O

o ifc>:? -Η

Η — W G TT H H - N _vC —— P - OH JJ II
I. '\ I. • I. I. i O = G G = O G π H OH N t f I. H H H O . I. Il . P - OH I.
H I. I. ° 6 ^H 5 OH

Example 4

In a 2 liter flask with a water cooler and a dropping funnel about 96 g (0.82 mol) of 70% orthophosphorous acid and 84 g (0.85 mol) of 37% hydrochloric acid are added. The received The mixture is then heated to boiling in the 2 l flask, while about 28.5 g (0.1 mol) of 2-aminoethyl isocyanuric acid, which was prepared as described in Example 1, is added. This addition takes place during "About 30 minutes, after which you add 60 ml of water to the reaction flask is added to obtain a homogeneous solution that has a boiling point of 108 ° C.

The clear solution obtained in the flask is kept boiling and 40 g (0.90 mol) of acetaldehyde are added over about 3 hours. After 3> -stündigen addition, the Keaktionsgemisch, which is a clear solution is cooled to 25 ⁰ G. A portion (50 g of approximately 308 g) of the solution is poured into 100 ml of methanol with stirring and a white precipitate is obtained. According to PiI-

-26-

209830/1197

the precipitate cake is triturated again in methanol Suspended, filtered and methanol rait into your filter washed. After drying, several g of white solids are obtained. The white solids are analyzed using the nuclear magnetic resonance spectrum (NMR) (which is the Shows presence of N-C-P bonds) and the elemental analysis is used. The white solid obtained contains essentially the isocyanuric acid derivative of the following formula: · ■

tl_ TT 0 f I.
H \ I. H H W. \ GH _x . 3 0 OH Xl 11 If G = O I. ¹ ι 3 It O = G G / _ /1 0 P - \ I. I. / - H H H OH H 0 OH ir P - i I. OH

Example 5

In a 2 1 flask equipped with a water condenser and 'dropping funnel, about 96 g (0.82 mol) brings a 70 / iige orthopkosphorige acid and 84- g (0.85 WOI) 37 / ^ ^e is hydrochloric acid. The ER- preserved mixture v; ith then heated to boiling while 26.5 S lrainoäthylisocyanursäure 2-about, as prepared in Example 1, zugxbt (Q '' Ί Mol?). The addition takes place over approximately 30 minutes. Then about 60 ml of water (after 30 minutes of addition) are added to the reaction. flask supplied in order to obtain a homogeneous solution »the

209830 / tt97

has a boiling point of approximately 108 ^° G.

The clear solution obtained in the ivolene is am biedeu held for about 5 hours, 52 g (0.90 hol) acetone added. iAfter the encore, this will be KeaKtionsgeuisch, which is a clear solution; is, cooled to 25 0, ijin i'eii (5 ^ g of about 320 g) of the solution is poured under itunren in 100 ml of methanol and one

holds a white precipitate. After filtering, the precipitate is slurried again in ethanol, filtered and the filter washed with methanol. After 'x' drying one obtains several GM; protein residues. The white solids are analyzed using P ^ KI-uv spectra (which show the presence of - G-Jr-joints) and by means of elementary analyzes. The white solid obtained essentially contains the isocyanuric acid derivative of the following formula

GH- O ' °

It

P-OH

C Hn y ''

N. '■■' / CH-OH

~ \ - I ^ ^{Γ λ1} \ οά-, ο

O = C "C = OHH \ ' ° "

\ S ' ■■■■ - ■ CP - OH

¹ ^. .CH ₂ .. OU

oalts of the various isocyanuric acid derivatives with which . 'concerned with the present invention, can be done by " "multiple neutralization of any of these isocyanuric acid- '

209830/1197 "^ '

COF ¹ Y
iAD ORIGIf

derivatives with a base which contains essentially the desired cation are prepared. For example, a sodium salt of one of the isocyanuric acid derivatives can be neutralized with a base containing the sodium cation, such as NaOH, Na ₂ OO ₅ and the like.

Example 6

Approximately 113 g (0.82 mol) of diethyl phosphite (CpH ₁ -O) pEHQ are placed in a 2 l flask equipped with a water condenser and dropping funnel. a .. The phosphite is then heated to about 100 g, while about 28.5 g (0.17 mol) of the 2-aminoethyl isocyanuric acid prepared according to Example 1 is added. The addition takes place over 10 minutes.

The mixture formed in the flask is kept at approximately 100 to 110 ^° C. and then 27 g (0.90 mol.) Of paraformaldehyde are added over approximately 3 hours. The reaction mixture is then cooled to 25.degree. The batch weighs 168 g and is an oily liquid. This oily liquid is analyzed by means of P ^ -KMR spectra and elementary analyzes. The material obtained is essentially the ester, which results from the following structural formula:

-29-

209830/1197

HO

Il rt -p _ r \ rt it

HH s " ·! ² '

·· 'y' H OGpH ₁ - ·

NO- CN ^ °

I I '·' V ^ HO

O = G C = Q H H ^ \ '"

jS CP-0C _o H _c

N ii «-

¹ H H.

Example 7

To the usefulness of isocyanuric acid derivatives in the context to explain the general formula I, the reaction products prepared in Examples 2 to 5 are the Subjected to sequestration procedures as described in the book Coordination Chemistry "Calcium Complexing By Phosphorus Compounds "by CF. Callis, A.F. Kerst and J.W. Lyons, Pp. 223-240, Plenum Press, 1969.

Approximately 1 g of each of the above-described reaction products (isocyanuric acid derivative "sequestrants") of Examples 2 to 5 is mixed individually and separately with 0.1% by weight of sodium oxalate in a 2 liter flask containing 1000 ml of water The value is adjusted to pg 11 in each case by adding sodium hydroxide. In each solution, which contains sequestering agents separately and individually, 0.1 molar calcium nitrate solution is titrated using a Dargent-Halmstadt automatic nitrator, model SE, the turbidity through

209830/119?

220098A

- 50 -

Light transmission is measured. The amount of calcium nitrate solution, added to each flask is sufficient to give sufficient indications as to diffraction in which the sequestering agent-containing solution changes from a relatively clear solution to a becomes cloudy. This zero angle indicates the amount of calcium that is produced by the respective sequestering agent is sequestered.

The results of the sequestering study on the reaction products of Examples 2 to 5 show that the various isocyanuric acid derivatives are good sequestering agents for calcium, this being one of the main undesirable cations in water used, for example, in cooling towers. In particular, it was found that the isocyanuric acid derivative prepared in Example 2 sequestered approximately 6 g of calcium per 100 g of isocyanuric acid derivative. It was further found that the other Isocyanursaurederivate of Examples 5 to $ i ⁿ a roughly equivalent ratio of calcium sequestered.

It is therefore one of the excellent uses of isocyanuric acid derivatives in the context of general Formula I, its use as a sequestering agent for the treatment of aqueous cysteines containing calcium ion, this treatment the formation of Jalcium-

-31-

20983Ü / 1 1 97

- 31 salt can prevent.

Example 8

In order to explain the usefulness of the esters of the isocyanuric acid derivatives, which fall within the range of general formula I, about 50 g of the ester prepared in Example 6 are mixed with an inert solvent (carbon tetrachloride) in a 500 ml beaker to produce a 10 wt. ^ ige solution to produce the ester. After the sludge has been produced, a separate, individual cloth sample of 7/6 × 7/6 cm in size made of undyed cotton cellulose is brought into intimate contact with the sludge by immersing the cloth sample in the urchlämrae for 5 minutes. The sample is then removed from the beaker containing this slurry and dried for 15 minutes in an oven maintained at a temperature of approximately 80 ^° C. After a period of l5 minutes at PQ C v / temperature ird increased and subjected to the cloth sample then for 10 minutes at a temperature of about 15O ⁰ C, to run to a reaction between the specific ester with the surface groups of the cotton cellulose.

The dried cloth sample made of "treated" cotton is tested for its fire retardancy, which is why attaching the cloth sample over a bunsen burner. The flame is adjusted so that the tip of the flame reaches

-32- 209830/1197

reaches about 2 cm below the treated cotton cloth sample; an "untreated" cotton sample is used as a control Used for comparison purposes. The Faüjmme is under everyone of each cotton sample (including the control) was held for about 35 indications and then removed. It will then visual observations are made. This experiment shows that the Konuroll sample, i.e. the cotton cloth sample, which has not been treated with any ester is completely destroyed. In contrast, the treated Cotton cloth sample primarily just charring and that Flame goes out within 5 seconds after removal of the bunsen burner from the test. It is easy to see from this that the esters of the isocyanuric acid derivatives im Framework of general formula I excellent in terms of its use as a fire retardant for cellulose material, for example cotton clothing are suitable.

The invention includes all deviations and changes from the examples, which are for the purpose of illustration only were given, insofar as the deviations make use of the general inventive concept.

- Patent claims -

201830/1197

Claims (1)

Patent claims: iv ^ esocyanuric acid derivative marked by the formula O R. O ir I &quot; ti G G - P t ι HN N OH ₀ CH ₀ N II ^{2 2} O = G G = O ■ \ R ^ 0 Il C - E - H ι. . wherein (a) R ^ and Rp are hydrogen and / or organic radicals are and (b) R ^ and R _{4 are} metal and / or aromatic ions, hydrogen, alkyl, alkenyl, aryl, alkylaryl, cyclic and / or alicyclic radicals. 2. Compound according to claim 1, characterized in that dali ic ,, Ro and R _{4 are} independently hydrogen. 5. Compound gbrcäß "claim 1 d. Adurchge indicates that R - and R _{4 are} independently vcoeinatjler an alkyl group rnifc Ί biu ¹ V Kohlensboffatornu. ■: - -34- 2 nights 9 8 3 O / I I 9 7 ' 4. Process for the preparation of an isocyanuric acid derivative, characterized in that a aqueous mixture with a ρττ value below about 4 forms , the (1) 2-aminoethyl isocyanuric acid, (2) an organic carbonyl compound, namely aldehydes and / or ketones and (3) a material containing phosphorus, viz (a) orthophosphorous acid, (b) a combination of PGl-. and H _? 0 and (c) a dialkyl phosphite ester in which the alkyl group Contains 1 to about 20 carbon atoms and subjecting the mixture to temperatures above about 70 ° C, thereby co-forming an isocyanuric acid derivative at least one N-C-P bond is formed. 5. The method according to claim 6, characterized in that that the mixture additionally contains at least a catalytic amount of halide ions for inhibition contains the oxidation of the orthophosphorous acid to orthophosphoric acid during the process. 20983U / 1 19?